JPS6283747A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the reduction in the density of developed cyan color by incorporating at least one kind of specified cyan dye forming coupler into a sensitive material. CONSTITUTION:At least one kind of cyan dye forming coupler represented by the formula is incorporated into a sensitive material. In the formula, R is >=6C branched chain alkyl or substituted alkyl, any usual substituent for alkyl may be used as the substituent, X is H or a group releasable by a coupling reaction with the oxidized product of an aromatic primary amine developing agent, and X is preferably H, Cl, an aliphatic or aromatic oxy group having preferably 0-30C atoms. The cyan coupler is used by 0.002-0.5mol per 1mol photosenstive silver halide in a layer into which the coupler is incorporated. Thus, high sensitivity is provided and the density of developed color is hardly reduced even when an exhausted bleaching soln. is used.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a novel cyan dye-forming coupler (
The present invention relates to a silver halide color photographic light-sensitive material which has high sensitivity, excellent color reproducibility, and improved processing suitability by using a cyan coupler (hereinafter referred to as a cyan coupler).

(Prior Art) When a silver halide color photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic-amine developer and a dye-forming coupler react to form a color image. In general, this method involves a color reproduction method using a subtractive color method, and images of colors of yellow, magenta, and cyan, which are complementary colors, are formed in the circles that reproduce blue, green, and reddish-violet, respectively. Phenol derivatives or naphthol derivatives are often used as couplers to form cyan images. In color photography, color-forming couplers are added to the developer solution or incorporated into a light-sensitive photographic emulsion layer or other color image-forming layer and react with the oxidized form of the color developer formed by development. This forms a non-diffusible dye.

The reaction between the coupler and the color developing agent takes place at the active sites of the coupler, and couplers with hydrogen atoms at the active sites are equivalent couplers, i.e., stoichiometrically, only .mu.mol of dye can be formed to form 7 mol of total dye. It requires a silver compound with a nucleus.

- A coupler having a group capable of leaving as an anion at the active site is a 2-equivalent coupler, that is, stoichiometrically only 2 moles of silver/silver oxide having a development nucleus are used to form 1 mole of dye. This is a coupler that is not required, and therefore, compared to μ-equivalent couplers, the silver halide ti in the photosensitive layer can be generally reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material. Image sharpness is improved.

Conventionally, phenolic couplers and naphthol couplers have been used as cyan dye-forming couplers. In particular, naphthol couplers have an absorption maximum (λ
max) is a long wavelength, has low absorption in the edge region, and has excellent color reproducibility.Many couplers with excellent color development have also been discovered, and have been widely put to practical use, especially in color negative light-sensitive materials.

However, many of these naphthol couplers, specifically co-alkylcarpamoyl/-naphthol couplers and phenolic couplers, are bleached or bleach-fixed during the bleach-fixing process in the color development process. If it is fatigued or has low oxidizing power, it has the disadvantage that sufficient color image density cannot be obtained. One of the causes of this phenomenon is said to be the reduction and fading of the cyan dye by ferrous ions generated during the bleaching or bleach-fixing process.

One of the purposes was to overcome this drawback by adding a ureido group to the 2nd position! Furthermore, phenolic couplers having all carbo/amide groups at the j-position are disclosed in JP-A No. 6-64'/JμC, No. 7-201Aj4c3, and No. 7-20≠j≠μ,
Same j7--〇≠jhiro! Same issue! f-332 hiro 2, same j
No. 1-33210 and the like. Such couplers are susceptible to fading of the color image by ferrous ions.
Although color images have the advantage of being robust against light, heat, and humidity, they have the disadvantage that the absorption spectrum of color images has large absorption in the edge region, which deteriorates color reproducibility. Because of this, it was difficult to say that it was necessarily suitable for the recent photosensitive materials with high sensitivity and excellent image quality.

On the other hand, U.S. Patent No. 3. The coarylcarpamoyl-l-naphthol-based cazolers described in 'Alt, IWE, etc. are said to have small absorption in the edge region of the absorption spectrum of the color image, and the color image fades due to ferrous ions. On the other hand, the maximum absorption wavelength (λm a x
) is significantly shifted to the shorter wavelength side, thus increasing absorption in the edge region and deteriorating color reproducibility.

(Problems to be Solved by the Present Invention) The first object of the present invention is to provide a halogen that exhibits an extremely small decrease in cyan coloring density even when using bleach or bleach constant H9t with weak oxidizing power during bleaching or recreational bleach constant blue processing. The purpose of the present invention is to provide a silver oxide color photographic material.

A second object of the present invention is to provide a silver halide color photographic material with high sensitivity and excellent image quality by using a new cyan coupler with excellent color forming properties.

A third object of the present invention is to provide a silver halide silver halide with excellent color reproducibility by using a new cyan coupler that has small absorption in the edge region of a cyan image and has a maximum absorption wavelength that is independent of the color density. Our objective is to provide color photographic materials.

(Means for Solving the Problems) These objects of the present invention are to provide a silver halide color photographic light-sensitive material having at least one layer of silver halide emulsion on a support. This was achieved by a color photographic light-sensitive material with a fluorogenated taste, which has a ftW characteristic by containing at least one cyan dye-forming coupler represented by the general formula CI).

General formula (1) In the formula, R is a branched alkyl or substituted alkyl group having 4 or more carbon atoms, and X is a hydrogen atom or a group separated by a D-coupling reaction with an oxidized product of an aromatic primary amine developer. represents a possible group. B' represents a group capable of substituting on the phenyl nucleus (excluding 0), and n represents an integer of 0. However, X is not a photographically useful group.

Conventionally, as a λ-arylcarbamoyl-7-naphthol coupler, for example, U.S. Pat.
It is known that the substituent of the aryl group at the 2-position of /-su7toll, ie, the ballast group (also referred to as a diffusion-resistant group), is a straight-chain alkoxy group, as in the compound described in No. Although this type of coupler has excellent features as mentioned above,
It had the disadvantage that the maximum absorption wavelength (2 m a x ) in the high color density region was significantly shifted to shorter wavelengths, and the absorption in the edge region was significantly increased. The present inventors conducted extensive research to solve this problem, and found that this drawback 1 could be overcome by changing the substituent group in general formula (1) to a branched chain alkyl group. Ta. The effect of such substituents was completely unexpected and surprising.

In addition, a coupler having a branched alkoxy group as a diffusion-resistant group is disclosed in JP-A No. 1L4-J031, but here we do not mention its application to co-arylcarpamoyl-/-su7toll couplers, nor do we give any suggestions thereof. The purpose of this method is to improve the solubility and dispersibility of the coupler, which is clearly different from the purpose of the present invention.

The compound represented by the general formula [I] will be described in more detail below.

In the general formula [I], R is a branched alkyl or substituted alkyl group having 6 or more carbon atoms, and as a substituent, all substituent groups commonly used for alkyl groups can be used. Specific examples of substituents include alkenyl groups, alkynyl groups, cycloalkyl groups, aromatic groups,
Heterocyclic group, norogen atom, aliphatic oxy group, aromatic oxy group, heterocyclic oxine group, aliphatic thio group, aromatic thio group, heterocyclic thio group, hydroxy group, carboxy group, sulfo group, cyano group group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, heterocyclic sulfinyl group, aliphatic ox7carbonyl group, acyloxy group, acyl group, carbamoyl group, sulfamoyl group , a carbonamide group, a sulfonamide group, a ureido group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, a carbamoyloxy group, and the like. Here, when the number of carbon layers of H is 4 or more, diffusion resistance is imparted to the coloring element.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer (hereinafter referred to as a leaving group). However, X is not a photographically useful group. Examples of leaving groups are halogeno atoms, sulfo groups, aliphatic oxy groups, aromatic oxy groups, ? J! Cuizuka oxy group,
Aliphatic thio group, aromatic thio group, acyloxy group, carbonamide group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, aliphatic oxycarbonyloxy group, aliphatic thiocarbonylamino group, carbamoyloxy group, nitrogen atom Examples include a heterocyclic group bonded to the coupling active position of the coupler. A photographically useful layer is a group that is separated by a coupling reaction and exerts a post-photographic effect (for example, a development inhibitor, a development accelerator, a silver halide solvent, a developing agent, a fogging agent, a reducing agent, a coupler, an antifogging agent, a bleaching agent, etc.). These include aromatic azo groups used in so-called colored couplers for color correction, which have absorption in a specific visible region by bonding with photographic dyes and coupler residues (accelerators, bleaching inhibitors, etc., and precursors thereof), and photographic dyes. Photographically useful group? If substituent X is not used, the photographically useful group acoustic coupler is added to the light-sensitive material in an amount within the range in which the optimum effect can be obtained. This is because, if enough t is added to obtain the desired effect, the amount added will be too large and the desired effect will not be obtained, resulting in a loss of photographic performance.

In the above, the aliphatic group refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Further, the aromatic group refers to a substituted or unsubstituted monocyclic or condensed ring aryl group, and the term heterocyclic group refers to all substituted or unsubstituted monocyclic or condensed ring heterocyclic groups. Examples of aliphatic groups include methyl group, ethyl group, t-7' thyl group, cyclohexyl group, 2-
Ethylhexyl group, n-decyl group, n-dodenyl group, 2
-hexyldecyl group, n-hexatecy group, 7lyl group,
Examples of aromatic groups include propargyl group, benzyl group, octadecenyl group, trifluoromethyl group, carboxymethyl group, methoxyethoxy group, dodenyloxycarbonylmethyl group, comethylsulfonylethyl group, phenyl group, naphthyl i, p Examples of heterocyclic groups include copyridyl group, hiro-pyridyl group, etc. Is, 2-7lyl group, coachenyl group, t-quinolyl L /-phenyl-jf trazolyl group, /-pyrazolyl group, /-imidazolyl group, ! , <4
-dioxoimidazolidin-3-yl group, benzotriazol-7-yl group, etc. can be mentioned, respectively.

Next, among the compounds represented by the general formula [I], compounds preferably used in the present invention will be described.

The oncv substitution position may be any of the ortho, meta, and para positions relative to C(JN)i in the general formula CI), but the ortho position is particularly preferred. The number of carbon atoms is preferably from t to 30, and a branched alkyl group is preferred.

X is preferably a frozen candy atom, a chlorine atom, an aliphatic group, or an aromatic group, and the number of carbon atoms thereof is O to 304. I can list the ones mentioned above. Examples of aliphatic oxygen groups include methoxy group, ethoxy group, cochloraethoxy7 group, cohydroxyethoxy7 group, comethoxyethoxy group, carpoquinmethoxy7 group, 3-carboxypro♂oxy group, comethoxychetoxycarpamoyl group. Methoxy group, l-carboxylene ethoxy group, 2-methylsulfonylethoxy group, comethylsulfonamidoethoxy group, co(carboxymethylthio)ethoxy group, 3
-(carboxymethylthio)propyloxy group etc. as an example of an aromatic oxy group, ≠-acetamidophenoxy7
group, 2-acetamidophenoxy group, goo(3-carboxyprop/amido)phenoxy group, ≠-methylsulfonylphenyl group, and the like.

Specific examples of 几' have the same meanings as the substituents allowed for R (excluding those represented by 0 above), and include carbamoyloxy groups below the alkenyl group.

The preferred value of n is 0 to 1.

Examples of compounds represented by the general formula CI) are shown below.

2H5 (!8) UCH2C:H2S0)i2C:00)iU (C1-
12) 3C(J(JH) The compound represented by the general formula [I] is
Kou 22, z2-ir Jir, 7.2-ta 093
No. 2, same! 3-1λμ23, same j3-/0!226
No., same jlfi-4clr No. 237, same j≠-t le/
Kota issue, same! No. j-32071, same! ! -Otsu! Ri No. 17, same! 6-7ri No. 3, same jA-7λt≠3 No., same j6
-λ71≠7, same! 6-126 the 3rd issue, same sr-ta! 3≠≦ and U.S. Pat. No. 3,1411, 1
It is synthesized by the method described in No. 93, etc. A synthesis example is shown below.

(Synthesis Example) Synthesis Example 1 Synthesis of Exemplified Compound (1) Cohexyldecanol 72.79, toluenesulfonic acid chloride 602, and Picgin 26°/f f2
Dissolve in 0mg of chloroform and heat under reflux for 6 hours.
-ta. The reaction solution 't (washed three times with 3 oomg of water and then concentrated to obtain oily 2-hexyldecyl para-toluenesulfonate r, I 10 fc.

2-acetamidophenol 4! ! ,≠f% Cohexyldecyl paratoluene sulfonate 1lO2 and potassium carbonate 62. /f dimethylformamide JOOml
Add gold at 7o"c! Heat and stir for hours. Add lIo to the reaction solution.
Add oml of ethyl acetate! It was washed three times with OO- water and then concentrated. The concentrate was purified using a chromatography column packed with silica gel using a mixed solvent of n-hexane and ethyl acetate as a developing solvent to obtain oily 2-(cohexyldecyloxy)acetanilide #, /f.

λ-(cohexyldecyloxy)acetanilide taro, 12 and salt production TW! 4! 210ml of ethanol in Hiroml
1f was added and heated under reflux for 3 hours. Add 30% ethyl acetate to the reaction solution.
The mixture was washed three times with 1 J of water and then concentrated to obtain 49.2 f of 2-(2-hexyldecyloxy)aniline in the form of an oil.

l-Human I:! Phenyl 7-2-naphthoate 23fA
Biko (2-hexyldecyloxy)anili/35?
The mixture was heated and stirred at izo°C for t hours under a nitrogen stream. Is the reaction solution filled with silica gel or a mud column? The desired oily illustrative coupler (1) ThJco9 was obtained by slugulation using n-hexane as a developing solvent.

Synthesis Example 2 Synthesis of Exemplified Compound (5) Instead of co-acetamidophenol, 3-acetamidophenol was prepared in the same manner as in Synthesis Example 1, but oily 3-(
Cohequin (rudecruoxy) aniline obtained (9, phenyl l-hydroxy-conaphthoate/? ? and 3-(cohexyldecyloxy7)72lJ
The mixture was heated and stirred at @c for μ hours under a nitrogen stream. The reaction solution was purified using a chromatography column filled with silica gel and using n-hexane as a developing solvent to obtain an oily target exemplified compound.

In the silver halide color photographic material of the present invention, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide.

Any silver halide, silver chloride or silver chloroiodide, may be used, and silver iodobromide is preferable for high-sensitivity light-sensitive materials. In the case of silver iodobromide, the silver iodide content is usually less than 100 molar, preferably less than 10 molar, more preferably less than 10 molar.

The above-mentioned silver halide grains may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape, or may have a twin crystal shape. There are crystal defects such as planes, and h is a composite form of these.

Also, mixtures of particles of various crystalline forms may be used.

The grain size of the silver halide mentioned above may be fine grains of about 70 microns or less, large grains with a projected area diameter of about 70 microns, or monodispersed emulsions with a narrow distribution.
Alternatively, a polydisperse emulsion having a wide distribution may be used.

Further, tabular grains having an aspect ratio of 1 or more may be used in the above emulsion layer.

The crystal structure of the emulsion grains described above may be uniform, the inside and outside may have different halogen compositions, or they may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1 IAA, US Patent No. 3,106,0
No. 41, same μ, Hirohiro.

No. 177 and patent application Sho jr-λ≠? It is disclosed in Kou No. 62, etc. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver rhodanide such as silver rhodanide and lead dispersion may be bonded.

The above-mentioned emulsion may be of the surface latent flaw type in which latent flaws are mainly formed on the surface, the internal latent image type in which latent flaws are formed inside the grains, or the type in which latent fM is present between the surface and the inside.

The silver halide photographic emulsion that can be used in the present invention can be produced using any known method, for example, Research Disclosure, Vol. 7, Al74μ3 (December 1971), pp. 22-23, "■.

Emulsion Preparation
and'rypes)'' and the same, vol. 117, If
, 11714 (January 2007), p. 6, 1 can be followed.

The photographic emulsion used in the present invention is "Physics and Chemistry of Photography" by Kide Guno7, published by Beaumontel, (P, Glaf
kids, Chimie et Physique
Photographque Paul Monte
l.

/rit7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin, Photo-
graphic emulsion chemis
try (Focal Press, / 5'46),
"Manufacture of photographic emulsions and cabinets" by Zelikman et al., published by Vol.
tal, Makingand Coa ng P
photographic emulsion.

It can be prepared by appropriately using the method described in Focal Press, /P 44C).

In preparing the photographic emulsion used in the present invention, various silver halide solvents (for example, ammonia, Rodankali, U.S. Pat. No. 3,271,117, JP-A-Sho!/-
/-340, JP-A No. 3-R2UOR, JP-A-Sho 13
-/u4AJIY issue, Tokukai Akira! Hiro-1007/7 issue or Tokukai Sho! The thioethers and thione compounds described in Hiromu/Jar Co. No. 1, etc.) can also be used.

As a ratio-dispersed emulsion, silver halide grains having an average grain diameter of greater than about 0.91 microns are used, and at least the! Emulsions whose weight is within ±≠0 inches of the average grain diameter are typical. The average particle diameter is O0λj-2 microns, and at least R! At least % by weight or (number of particles)! The average grain diameter of silver halide grains is ±2.
Emulsions such as those within the 0 fb range can be used in the present invention.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium +11 or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in these processes are based on the research mentioned above.
Disclosure Ji/744c3 (/!77 for 1 year)
February) and Wholesaler/17/l, (/De7//Month), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the amounts listed in the table below.

Additive type 'B, DI74143 BD/17
/ll Chemical sensitizer page 23, page 1, right column
Sensitivity enhancer Same as above 3 Spectral sensitizer,
23～λ≠Page 1st page right column～Supersensitizer
1st right column ≠ Whitening agent C section! Antifogging agent λμ~2! Page 6 Related page right column and stabilizer B Light absorber, page 21-26 Page 1 right column ~ Ilter dye Page 410 left column Ultraviolet absorber 7 Stain inhibitor λj negative right column 6! O page left to right column l
Dye 1 - Image stabilizer page 25 ta Hardener page 26 tri negative left column io
Binder Korosada Same as above/l Plasticizer, lubricant Koasada ≦! Page Q, right column l Coating aid,
Table 24-. Page 27 Same as the above surface active agent As the yellow coupler that can be used in the present invention, a typical example is a hydrophobic acylacetamide coupler having a pallast group. A specific example is US Patent No. 2.
u07, lio issue, same number 2゜17! , No. 017 and No. J, 24j, jO6, etc. The use of two-equivalent yellow couplers is preferred for the present invention;
U.S. Patent No. 3゜≠011. /riμ issue, same number 3.1, 9
No. 21, same No. J, ? JJ,! 0/issue oyohi same number! , 022゜6.20, etc., the oxygen atom separation type yellow coupler or Tokko Sho! l-1073
No. 2, U.S. Patent No. Hiroshi, ≠0/, 7 Jr.
2A, No. 0217, R1)/rOjJ (/97W year'
January), British Patent No. 1. ≠21.0.20, West German Application Publication No.
No. 329, 1117 and Co.

A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 33,112. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably a hydrophobic i/dazolo type or cyanoacetyl type coupler having a ballast group. - Pyrazolone and pyrazoloazole couplers may be mentioned. ! -2 Lasolone couplers are preferably those in which the 3-position is substituted with an arylamino group or an acylamino group in view of the hue of the coloring dye and the intensity of the color.
3/ /, No. 012, No. 2.3≠! , No. 703, No. 2,400,711, No. J, 901, 77
No. 3, No. 3, Otsuko, No. 413, No. 3. /! Ko, t
No. 6 and No. 3, 93 &, 01. is written in the number etc. Double duty! As the leaving group of the pyrazoan coupler, the nitrogen atom leaving group described in U.S. Pat. No. 310.61 or the arylthio group described in U.S. Pat. preferable. Also, the palast fundamental sound described in European Patent No. 73°634! −
Pyrazolone couplers provide high color density. As a pyrazole a7zole coupler, U.S. Patent No. 3゜04
1, the pyrazolobenzimidazoles described in Ko 32, preferably the 9-pyrazolo(j,/-c)(/) described in US Pat. No. 3,7, otZ.

[Co, μ] Triazoles, Research Disclosure A≠CocoO
73! ! Virazolotetrazoles described in No. 4 and Research Disclosure, MuJ4CJj7 (/4F
Examples include pyrazolosilazoles described in JP-A No. 60-3 Otsuko No. 9). U.S. Pat.
00.

The imidazo(/, cob) pyrazoles described in EP 1/9.rtOA are preferred, and the pyrazolo(/, t-b)(/, co, hiro) triazoles described in EP 1/9.rtOA are particularly preferred.

Examples of cyan couplers that can be used in combination with the cyan coupler of the present invention include the naphthol couplers described in U.S. Pat. Ko,
2/2 issue, μ, l hiro 6゜396, hiro no. 221
Typical examples include the oxygen atom detachment type double-attached naphthol couplers described in No. 233 and No. 294,200. Further, a specific list of phenolic couplers is disclosed in US Ti Patent No. 2,362. Pλri No., same No. λ.

roi, /7/No. 2,772,142, No. 2. It is described in rqr, r26, etc.

Cyan couplers that are robust to humidity and temperature are preferably used in combination, and are typically described in U.S. Patent No. 3. i
Bow, No. 622, same No. ≠,! 33゜Tatata, same No. 4
The phenylureido radical sound is present in the co-position described in Lj/, ryu No. 2 and the same No. 27,767!
These include phenolic couplers having acylamino ibt in the - position.

In order to correct unnecessary absorption of color foci, it is preferable to use a colored coupler together with the color negative photosensitive material for bridges to perform masking. Colored couplers are based on the research mentioned above.
Disclosure, ya/7t≠3, ■~G terms are subject to change.

A coupler like this, which can improve graininess when used in combination with a coupler that has a color-forming dye and a diffuse acoustic effect, is
US Patent @Hiroshi, 36bu, 237 and British Patent No. 2,
12! Specific examples of magenta couplers are given in European Patent No. 2t, 170 and West German Application No. 3, 170.
No. 23≠, No. 333 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form electrocombinants as described above. Typical examples of polymerized nine-dye-forming cazolas are described in U.S. Patent No. 3. 'Aj/, 1
r20 and 閤mtA, oro.

It is described in No. 277. Specific examples of polymerized magenta couplers are described in British Patent Nos. 2,10, 173 and US [i! ff 4', J g 7, . Self-published on 2rx-q.

Couplers that upon coupling release onto photographically useful residues can also be preferably used in the present invention. As the DI coupler that releases a development inhibitor, the patented coupler described in the aforementioned Research Disclosure, Mu/7tμ3, Items 4-2 is useful.

In the cyan coupler of the present invention, the objects of the present invention can be achieved by using 7 moles, 0.002 to 0.1 mole, of the r-photosensitive silver halide to be introduced.

The coupler of the present invention and the couplers that can be used in combination can be introduced into the photosensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. can be cited as a typical example. In the oil-in-water dispersion method, the boiling point is /7
! After dissolving in either a high boiling point organic solvent of C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling organic solvents are described in U.S. Pat. It may be used for application after being removed or reduced by a filtration method or the like.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol polymer conductors, ascorbic acid conductors, colorless couplers, and sulfone as color antifogging agents or color mixing inhibitors. It may also contain amidophenol derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Examples of organic antifading agents include 'o+/y, b-hydroxychroma 7KAs, monohydroxycoumarans, spirochroman a, p-alkoxyphenols, bisphenols, hindered phenols centered on gold, gallic acid derivatives, Typical examples include methylenedioquine benzenes, aminephenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Furthermore, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex may also be used. other,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a pack layer.

The color photographic light-sensitive material according to the present invention is the arS-2? The development process can be carried out by the usual method described in the left column to the right column of page 1 and 16iryit. The color photographic material of the present invention is usually washed with water or stabilized after developing, bleach-fixing or fixing.
give

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-7-11≠3 instead of the water washing step. In the case of this step, a two-tank countercurrent column is required. Various compounds are added to the main stabilization bath for the purpose of stabilizing the image. For example, membrane pH'
Various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide) for adjusting ft (e.g. pH 3-r), IJum, ammonia water monocarboxylic acid, dicarboxylic acid, polycarboxylic acid (used in combination with gold) or hol? Typical examples include IJ. In addition, if necessary, water softeners (inorganic phosphoric acid, aminophoricarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) All of the additives (benzimidazoles, halogenated phenols, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, or two or more compounds for the same or different purposes may be used in combination. It's okay.

f&, membrane pH after treatment It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a pH adjusting agent.

The present invention can be applied to plum color photosensitive materials. color reversal film for slides or television;
Typical examples include color reversal paper and color reversal paper. The present invention can also be applied to a black-and-white photographic material using a mixed three-color coupler as described in Research Disclosure 417/23 (July 2007).

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 A light-sensitive material, samples ioi to l//, having each layer having the composition shown below was prepared on a cellulose triacetate support. The couplers contained in the first layer are shown in Table-7.

1st layer: Silver iodobromide emulsion (IIi iodide!!≠mol 1) Amount of silver coating
/, 444s7m 2 Sensitizing dye I μ, j x 10 mol per mol of silver Sensitizing dye ■ /, j x 10 mol coupler (table/) A per mol of silver, O x / 0 moles No. 11i: Protective layer polymethyl methacrylate particles (diameter approximately 1.

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each gelatin layer containing 1 μm).

Compound sensitizing dye I used to prepare the sample: anhydro-j, j'-dichloro-J,
J'-G(r-sulfopropyl)-? -Ethylthiacarzecyanine hydroxide-pyridinium salt color XII; ,μ′−! '-Dibenzothiacarbocyanine hydroxide triethylamine salt) 1-i: (OH2=CH802CH2GU
N) icH2±2 After exposing the obtained samples 10/ to /// to light for sensitometry, the following development treatment (A) was performed at JR'C.

/ Color development ・Old...Original... 3 minutes!
Second 2 Bleach ・Old...Old... “6 minutes 30
Second 3 Water Wash Town... Decoy... 3 minutes! seconds μ
Fixed... River... Old... Hirobu 20 seconds!
Wash with water ・・・・・・・・・・・・ 3 minutes!
Second 6 Stable...Town...l 1 minute! The composition of the treatment liquid used in each step is as follows.

Color Developer Sodium Nitrilotriacetate / Of Sodium Sulfite Sodium Carbonate 30. θ2 potassium bromide
/, Hiro? Hydroxylamide 7 sulfate a salt λ,≠2≠-(N-ethylhe β-hydroxyethylamino) -λ-methylaniline sulfate g,
evening? Add water, l bleach solution ammonium bromide/1.0. Of ammonia water (214) Coj, Occ ethylenediamine-tetraacetic acid sodium iron salt /J0. Of glacial acetic acid
/4A, add Occ water
il fixer sodium tetrapolyphosphate
λ, Of sodium sulfite
μ, 01 ammonium thiosulfate (717%) /
7! ,Occ Sodium Biphosphite France,
61 Add water to make IL stabilizer formalin 1. Add OcC water /l -Next, development processing CB) was carried out in the same manner as development processing (A) except that the bleaching processing solution in development processing (A) was changed to the following processing solution formulation. . This bleaching solution is a schematic representation of a state in which a large amount of photosensitive material has been processed and is exhausted.

Processing step CB) Bleach solution composition (D-2) Pour steel wool into (D-2), seal it tightly, and leave it for Fe (11)-EDTAt-Fe (■)-EDTA
After that, it was treated in the same manner as in treatment step (A), except that it was added to this /oopRgt-CD-/) to prepare a bleaching solution in treatment step CB).

Sample 10/treated in treatment steps (A) and CB)
The density was measured using red light and green light for ~/// (a self-recording densitometer manufactured by Fuji Photo Film Co., Ltd. was of course used).

The results are shown in Table-7.

The dye residual rate in i-/ is defined by the following formula.

Relative sensitivity is the total relative value of the reciprocal of the exposure amount required to increase the total density corresponding to [minimum density + 0.2], expressed in true form. Also, the red density is O6! The green density ratio at a red density of 2.0 and the green density ratio at a red density of 2.0 are each defined by the following equations.

Green density ratio at red go and r; red density 09! green color III degree 10. j￥, 100 red density ko, green density ratio at 0 = green density at red density 2.0/ko, OXl 00 Table-7
As is clear from the above, the sample of the present invention has a small decrease in red density in a tired bleaching solution, high sensitivity, little unnecessary absorption in the edge area, and even when the red density changes, the red density in the edge area remains unchanged. It has the feature of little change in absorption.

Comparative Couplers Example 2 Sample λ0/-20 was prepared in exactly the same manner as in Example 2, except that only the cazoler contained in the first layer was changed. ? The obtained sample was exposed to light for sensitometry in exactly the same manner as in Example 1, and then developed (A) and (-B'J'
It was done at kjl'C.

The results are shown in Table-2.

From Table 2, samples of the present invention [20μ~20! ] clearly achieves the object of the present invention.

Crust coupler (JC) 12C) 12802C) i3 Example 3 Multilayer color photosensitive material 30 consisting of each layer having the composition shown below on a cellulose triacetate film support.
/ was created.

(Sample 301) 1st layer: antihalation layer, gelatin layer containing black coquid silver λth layer: intermediate layer λ,! - Gelatin layer #31 containing an emulsified dispersion of D-t-octylhydroginone; first red-sensitive emulsion layer silver iodobromide emulsion (silver iodide; j molar ratio)...
・・・Silver coating t i, 4q7m2 Sensitizing dye■・・・・・・・・・・・・Hiroshi, jxio mole sensitizing dye for 1 mole of silver■・・・・・・・・・・・・・For 1 mol of silver/, jXlo Mol coupler EX-1...0.03 mol for 1 mol of silver Coupler EX-CO...0.003 mol for 1 mol of silver Coupler EX-J...Silver 0.000f for 7 moles
Mol first layer; red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 70 mol%)...
・Silver coating 17/, 41f/m2 Sensitizing dye l・・・・・・・・・3×to-'mol sensitizing dye for 1 mole of silver■・・・・・・・・・...per 1 mole of silver/x10 mole coupler D...00 per mole of silver.
0λ comol coupler EX-2...0.00/6 per mole of silver
Mol number! Layer; 6th layer same as the 2nd intermediate layer; 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; μmol%)...
・・・Silver coating amount /, 2f/m” Sensitizing dye■・・・・・・・・・・・・For 1 mole of silver!×10-' mol sensitizing dye■・・・・・・....lambda x 10-' molar coupler for 1 mole of silver EX-μ...o, or molar coupler for 1 mole of silver EX-r...o, oor molar coupler for 1 mole of silver -bX-b...0.00/r per mole of silver
Mol No. 7 Iso; Second green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; r malt...
・Silver coating amount t, 397 m” Sensitizing dye ■・・・・・・・・・・・・ For 1 mole of silver! × 10-' mol Sensitizing dye ■・・・・・・・・・・・・... @ per mole/, 2X10' mole coupler-EX-7... 0.0/7 mole per mole of silver Coupler EX-r... 0.003 mole number r per mole of silver Layer: yellow filter, yellow colloidal silver and gelatin aqueous solution, J-G-T-
gelatin layer containing an emulsified dispersion of octylhydroquinone; second green-sensitive emulsion layer; silver iodobromide emulsion (silver iodide; 6 mol);
...Silver coating 'fj O,7f/m'' Coupler EX-t...0.2 tamol for 1 mole of silver Coupler EX-tO...o, oi tamol for 7 moles of silver ior@; λth evening-sensitive emulsion layer silver iodobromide (silver iodide; 6 mol%)
・Silver coating amount o, 4 f/m" Coupler EX-ta... 0.06 mol per 1 mol of silver 11th layer; 1st protective layer Silver iodobromide (silver iodide/-1: ruti, Average particle size 0.07μ)
・・・・・・・・・Amount of silver coating o, zy7
Gelatin layer 121@, entirely containing an emulsified dispersion of m2 ultraviolet absorber UV-t; λth protective layer gelatin layer containing polymethyl methacrylate particles (diameter approx. 1.!μ) gold coating.

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer.

The sample prepared as described above was designated as sample 30/.

Compound sensitizing dye used to prepare the sample; A/Human rotor ethyl! ,! l-dichloro-3,3'-di(r-sulfopropyl)oxacarbocyanine sodium salt sensitizing dye ■; anhydro-
! ,t,! ',G'-tetrachloro-i,i'-diethyl-3,3'-cy(β-[β-(r-sulfopropoquine)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt EX-/1C3H11 EX -2 EX-j EX-μ EX-b α Coupler EX-7 Coupler J!: X-r α Casolar EX-5' EX-7.

UV-/x/y=7/3 (weight ratio) Coupler CD) k of sample 301 Equimolar substitution shown in Table 3 was performed to prepare samples 302 to 307''.

The obtained sample JO/~307 was subjected to SE/7 tometry exposure, and then developed in the same manner as in Example 2, using a new solution and Roshi that had deteriorated due to long-term continuous operation. The total concentration of the escaped sample was measured using red light.

The results are shown in Table-3.

From Table 3, compared to the samples (30/-303) using comparative couplers (1)) to [F], the samples of the present invention (30/-303)
01) has high sensitivity and color development with tired bleach solution 1
The decrease of 4 degrees is also extremely small, and the effect of the present invention is clear.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, which contains at least one cyan dye-forming coupler represented by the general formula [I]. A silver halide color photographic material characterized by: General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R is a branched alkyl or substituted alkyl group having 6 or more carbon atoms, and X is a hydrogen atom or aromatic primary amine development Represents a group that can be separated by a coupling reaction with an oxidized drug. R' is a group capable of substituting a phenyl nucleus (
(excluding OR), and n represents an integer from 0 to 4. However, X is not a photographically useful group.